TWI666336B - Method of selectively depositing a material on a substrate - Google Patents

Abstract

The present invention provides a method for selectively depositing a material on a surface of a substrate with respect to a different second surface. An exemplary deposition methods may include: with respect to a second surface different (e.g., H-terminated surface) of the substrate, the first selective surface (e.g. the surface of SiO ₂₎ is deposited on the same substrate material, for example comprising nickel, nitrogen Nickel, cobalt, iron, and / or titanium oxide materials. The method may include processing a surface of the substrate to provide an H-terminus prior to deposition.

Description

Method for selectively depositing material on substrate

This application claims the priority of U.S. Provisional Application No. 62 / 111,508 (named "SELECTIVE DEPOSITION") filed on February 3, 2015, and the full disclosure content of the said U.S. Provisional Application Incorporated into this case for reference.

The present invention relates to selective deposition performed on a first surface of a substrate opposite to a second surface. Further, further processing may be used to subsequently deposit a different material on the second surface relative to the first surface.

Selective deposition processes are needed in the semiconductor industry for making smaller and smaller structures.

Integrated circuits are currently manufactured by a complicated process in which various material layers are sequentially constructed in a predetermined arrangement on a semiconductor substrate.

A predetermined arrangement of the material on the substrate is often achieved by depositing a material over the entire surface of the semiconductor substrate and then removing the material from a predetermined area of the substrate (eg, by depositing a masking layer and a subsequent selective etching process).

In some cases, this can be reduced by using a selective deposition process. The number of steps of fabricating a surface of a compact on a substrate, wherein a material is selectively deposited on a first surface opposite a second surface. It is well known that it is very difficult to achieve selective deposition by a vapor deposition process such as atomic layer deposition (ALD). Generally, a long carbon chain self-assembled monolayer (SAM) is used to direct membrane growth on a selected surface.

In some aspects, a deposition method is provided. In some embodiments, a substrate including a first surface and a different second surface may be provided. In some embodiments, the first surface includes at least one AH _x end cap, where A is one or more of nitrogen, oxygen, or sulfur, and x is 1 to 2, and the second surface is hydrogen (H) Capped surface. In some embodiments, the substrate may be brought into contact with a first gas phase precursor including nickel (Ni), titanium (Ti), iron (Fe), or cobalt (Co), thereby opposing the second surface of the substrate, A material comprising nickel, titanium, iron or cobalt is selectively deposited on the first surface of the same substrate. In some embodiments, the selectively deposited material may include nickel or cobalt. In some embodiments, the deposition method may further include: contacting the substrate with the second gas-phase reactant. In some embodiments, the H-terminated second surface may be formed by processing at least a portion of a substrate surface before depositing a thin film. In some embodiments, the H-terminated second surface may be formed by treating at least a portion of the substrate surface with a hydrofluoric acid (HF) etch. In some embodiments, the H-terminated second surface may be formed by treating at least a portion of the substrate surface with a silicon compound, the silicon compound comprising ClSiH ₃ or (R ^I R ^II N) SiH ₃ , where R ^I and R ^{II are} independently selected from C ₁ -C ₄ alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and the like. In some embodiments, the first surface may include at least one OH end cap. In some embodiments, the first surface may include SiO ₂ . In some embodiments, the first surface may be a low-K insulator. In some embodiments, the first surface may include silicon oxide, silicon nitride, silicon oxynitride, fluorinated silica glass (FSG), carbon-doped silicon oxide, or another containing at least 50% silicon oxide. material. In some embodiments, the second surface may include -SiH ₃ , -SiH ₂ , or -SiH surface termination. In certain embodiments, a material comprising nickel, titanium, iron, or cobalt can be selectively deposited on a first surface opposite to the H-terminated second surface with a selectivity of at least 90%. In some embodiments, the deposition method may be an atomic layer deposition (ALD) or chemical vapor deposition (CVD) process.

In some aspects, a method is provided for selectively depositing a material comprising nickel, titanium, iron, or cobalt on a substrate. In some embodiments, a substrate including a first surface may be provided, the first surface including silicon oxide. In some embodiments, at least a portion of the first surface may be etched to thereby provide an H-capped second surface. In some embodiments, a material comprising nickel, titanium, iron, or cobalt may be selectively deposited on the first surface of silicon oxide relative to the second surface terminated by H. In certain embodiments, the selectively depositing a material comprising nickel, titanium, iron, or cobalt comprises: selectively depositing until a desired thickness of a material comprising nickel, titanium, iron, or cobalt is formed. In some embodiments, the method for selectively depositing a material including nickel, titanium, iron, or cobalt may be an atomic layer deposition or a chemical vapor deposition process. In some embodiments, etching at least a portion of the first surface may include exposing a portion of the first surface to HF. In certain embodiments, the selectivity may be at least 90% on the first surface relative to the H-capped second surface The material comprising nickel, titanium, iron, or cobalt is deposited.

In some aspects, a method is provided for selectively forming SiO ₂ on a substrate. In some embodiments, the method may include selectively depositing a material including nickel, titanium, iron, or cobalt on a first surface of the same substrate with respect to a different H-terminated second surface of the substrate, wherein The first surface includes at least AH _x end caps, where A is one or more of oxygen, nitrogen, and sulfur, and x is 1 to 2. SiO ₂ may be selectively deposited on the second surface of the H-terminus of the same substrate with respect to the first surface of the substrate. In some embodiments, a method may include etching a substrate to remove a material including nickel, titanium, iron, or cobalt from the substrate. In some embodiments, etching the substrate may include exposing the substrate to at least one of HCl, HNO ₃ or H ₂ SO ₄ : H ₂ O ₂ . In some embodiments, the first surface may include an OH-terminated surface. In some embodiments, the first surface may include silicon oxide. In some embodiments, the second surface may include a -SiH, -SiH ₂ or -SiH ₃ surface cap. In some embodiments, SiO ₂ may be deposited on the second surface of the substrate with respect to the first surface by plasma-enhanced atomic layer deposition (PEALD) or a thermal atomic layer deposition process.

100‧‧‧ Atomic Layer Deposition Process (Deposition Process)

110, 120, 130, 140, 150, 160, 170‧‧‧ steps

210, 220, 230‧‧‧ steps

310, 320, 330‧‧‧ steps

410, 420, 430‧‧‧ steps

510, 520, 530‧‧‧ steps

610, 620, 630‧‧‧ steps

710‧‧‧First surface

720‧‧‧Second surface

The invention will be better understood by reading the embodiments and the accompanying drawings, which are intended to illustrate the invention rather than to limit the invention, and in the drawings: FIG. 1 illustrates a different second surface for use with respect to a substrate, A flow chart of a deposition process for selectively depositing materials such as nickel metal, nickel nitride (NiN _x ), cobalt, iron, or titanium oxide on the first surface of the same substrate.

FIG. 2 illustrates a flowchart of a deposition process for selectively depositing nickel on a first surface of the same substrate with respect to a different second surface of the substrate.

FIG. 3 illustrates a flow chart of a deposition process for selectively depositing nickel nitride (NiN _x ) on a first surface of the same substrate with respect to a different second surface of the substrate.

FIG. 4 illustrates a flow chart of a deposition process for selectively depositing cobalt on a first surface of the same substrate with respect to a different second surface of the substrate.

5 illustrates a flow chart of a deposition process for selectively depositing iron on a first surface of the same substrate with respect to a different second surface of the substrate.

6 illustrates a flow chart of a deposition process for selectively depositing titanium oxide on a first surface of the same substrate with respect to a different second surface of the substrate.

FIG. 7 illustrates a nickel film selectively deposited on the first surface of the first substrate with respect to the second surface different from the first substrate and the second substrate according to an exemplary process as described herein.

In some cases, it is desirable to selectively deposit material on one surface of the same substrate (as opposed to a different second surface of the substrate). For example, selective deposition may be used to form a capping layer, a barrier layer, an etch stop layer, a sacrificial layer, and / or a protective layer or, for example, for sealing pores in a porous low-k material.

In certain embodiments, the processes described herein can be used to selectively grow materials including nickel, titanium, iron, or cobalt on SiO ₂ -based surfaces and other surfaces as described herein, such as nickel metal, nitride Nickel or NiN _x , cobalt, iron or titanium oxide structure. The nickel nitride or NiN _x described herein means a material containing at least some Ni-N bonds.

In some embodiments, a first material, such as a material including nickel, titanium, iron, or cobalt, such as nickel, nickel nitride, or NiN, may be selectively deposited on the first surface relative to a different second surface. _x , cobalt, iron, or titanium oxide film. For example, it can be selectively on the surface of a low-k insulator of the same substrate (such as an oxide or nitride surface, such as in the form of silicon oxide or silicon nitride), relative to the second surface of the substrate (such as an H-terminated surface). A film of nickel, nickel nitride, cobalt, iron, or titanium oxide is deposited thereon.

In some embodiments, the first surface for selective deposition includes AH _x capping, where A is one or more of nitrogen, oxygen, or sulfur, and x is 1 to 2. In some embodiments, the first surface comprises an OH end cap. In certain embodiments, the first surface is a surface capping e.g. NH _x -NH ₂ or -NH-terminated surfaces. In some embodiments, the first surface is a SH _x capped surface.

In some embodiments, the first surface is a dielectric surface, such as a SiO ₂ surface or a silicon oxynitride surface. In some embodiments, the first surface may include silicon oxide, silicon nitride, silicon oxynitride, fluoro-silicon glass (FSG), carbon doped silicon oxide (SiOC), and / or comprise greater than about 50 % Silicon oxide material. In some embodiments, the first surface includes OH groups, and may include, for example, an alumina (Al ₂ O ₃ ) surface having an -OH surface group.

In some embodiments, the second surface is a -SiH ₃ , -SiH _2, or -SiH surface. In some embodiments, the second surface is formed by etching a native oxide of silicon, and the second surface includes a Si-H bond. In some embodiments, the second surface is a pure silicon surface.

In certain embodiments, one or more surfaces may be treated to enhance or reduce deposition on the treated surface (as opposed to a different second surface). In certain embodiments, the first surface may be treated or activated to enhance deposition on the first surface (as opposed to one or more different surfaces). In some embodiments, a portion of the first surface may be treated or deactivated to reduce deposition on a treated portion (as opposed to an untreated portion of the first surface) of the first surface. In some embodiments, the second surface may be treated or deactivated to reduce deposition on the second surface (relative to the first surface of the substrate). In some embodiments, the first surface is treated to enhance deposition, and the second surface is treated to reduce deposition, thereby increasing selective deposition on the first surface (as opposed to the second surface).

In some embodiments, the H-terminated second surface relative to the substrate (eg, a second surface containing -SiH ₃ , -SiH ₂ , or -SiH), the first surface as described above (eg, a low-k insulator) surface, for example, is deposited on the oxide surface) comprising nickel, titanium, iron, or cobalt material, e.g., nickel (NiN _x) nitride, cobalt, iron, or titanium oxide layer. In some embodiments, the first surface is a SiO ₂ surface of the substrate. The second surface may be treated before or at the beginning of the deposition process of a material containing nickel, titanium, iron, or cobalt, such as nickel, nickel nitride (NiN _x ), cobalt, iron, or titanium oxide, by An H-terminus is formed on the second surface to reduce deposition on the second surface (relative to the first surface). That is, a first surface (e.g., SiO ₂₎ may be selectively deposited on the treated with respect, to the second surfactant is increased.

In certain embodiments, the surface of a first substrate comprising a dielectric material (such as SiO ₂ , another oxide, or another material as described herein) is treated such that the nickel, titanium, iron, or cobalt-containing Deposition or reduction of material deposition on one or more portions of the substrate. For example, one may be treated first surface of the substrate to form a second or more portions of the surface of H-terminated, e.g. -SiH _3, -SiH _2, or -SiH terminated surface. In some embodiments, the one or more portions of the first surface are treated with HF to form an H-capped second surface in the region.

In certain embodiments, by reacting a portion of the first surface (such as a portion of the SiO ₂ surface or other oxide surface) as described herein with a silicon compound to form a group comprising -SiH ₃ , -SiH ₂ or SiH The second surface of the mass to deactivate the portion of the surface. Such silicon compounds may include, for example, ClSiH ₃ or (R ^I R ^II N) SiH ₃ .

After being processed to form the H-terminated second surface, nickel may be selectively deposited on the remaining first surface (such as the surface of the first oxide (eg, SiO ₂ )) relative to the H-terminated second surface. , Titanium, iron, or cobalt.

In some embodiments, the deactivation process does not involve the formation of a self-assembled monolayer (SAM). In certain embodiments, the deactivation treatment does not include treatment with organic reagents.

In certain embodiments, H can be treated terminated surface (e.g., -SiH _3, -SiH _2, or -SiH terminated surface) of the part, to facilitate (with respect to the portion of the surface of the treated untreated surface) comprising the selective deposition of nickel, titanium, iron, or cobalt material (e.g., nickel (NiN _x nitride), cobalt, iron, or titanium oxide film). For example, a portion of an H-terminated surface, such as an etched silicon surface (SiH _x ), may be treated to provide a hydrophilic OH termination on the treated portion of the surface. The OH-terminated surface can be reacted with a nickel, cobalt, iron, or titanium precursor as described herein. Therefore, in certain embodiments, OH capping (or other capping as described herein) may be provided to enhance the deposition of nickel-containing deposits on the OH capped portion of the surface (as opposed to the remaining H capped second surface). , Titanium, iron or cobalt.

A first surface (such as a surface described herein) for selectively depositing a material (eg, SiO ₂ , other oxides, or other materials) may include a hydroxyl or OH group, which may have the effect of making the surface hydrophilic. Such surface capping of OH groups can naturally occur when the surface is exposed to ambient conditions, such as the atmosphere containing water. In some embodiments, at least a portion of the substrate surface may be treated to provide a first hydrophilic OH-terminated surface. In certain embodiments, at least a portion of the hydrophilic OH-terminated surface may be treated to increase the amount of OH groups on the surface. For example, the surface may be exposed to water (H ₂ O) vapor to increase the number of OH groups at the surface. In some embodiments, at least a portion of the surface of the silicon substrate is exposed to air and / or moisture (eg, an atmosphere containing water) to provide a first surface that is hydrophilic and includes at least some OH groups. In some embodiments, the hydrophilic surface is not treated prior to sedimentation.

In certain embodiments, at least a portion of the OH-terminated surface (or other first surface as described herein) may be treated to inhibit the deposition thereon of materials including nickel, titanium, iron, or cobalt (e.g., Nickel, nickel nitride (NiN _x ), cobalt, iron, or titanium oxide). For example, at least a portion of the OH-terminated first surface may be contacted with HF to provide an H-terminus and thereby provide an H-terminated second surface. In certain embodiments, the SiO ₂ surface is etched with HF (eg, 0.5% HF) to provide a SiH _x surface at the etched portion of the SiO ₂ surface. As described above, the portion of the first surface may also be treated by reacting the OH-first surface with a silicon compound to form a Si-H group on a portion of the first surface. Such silicon compounds may include, for example, ClSiH ₃ or (R ^I R ^II N) SiH ₃ , where R ^I and R ^II may be independently selected from C ₁ -C ₅ alkyl. OH-terminated surface (or first surface of the other such as described herein) into the surface of H-terminated surface can be suppressed with respect to the first surface of a substrate such as SiO ₂ (or first surface of the other such as described herein), for example, in A material comprising nickel, titanium, iron, or cobalt (eg, nickel, nickel nitride, cobalt, iron, or titanium oxide) is deposited on the treated portion of the surface.

In some embodiments, a semiconductor substrate including a dielectric (eg, SiO ₂ ) is provided. A portion of the surface can be selectively etched by exposure to HF (e.g., 0.5% HF), thereby forming a first surface including SiO ₂ and an etched portion of the first surface of SiO ₂ including hydrogen-terminated silicon a second surface (e.g. -SiH _3, -SiH ₂ -Si-H, or surface). Then selectively surface comprising a first SiO ₂ (relative to the second surface of H-terminated) comprises depositing a nickel, titanium, iron, or cobalt material, e.g., nickel (NiN _x) nitride, cobalt, Iron, or titanium oxide film.

In some embodiments, a semiconductor substrate including a dielectric (eg, SiO ₂ ) is provided. A portion of the surface may be selectively exposed to a silicon compound (e.g., ClSiH ₃ , (R ^I R ^II N) ₂ SiH ₂ , X _y SiH _4-y , (R ^I R ^II N) _y SiH, as described herein _4-y , (R ^I R ^II N) SiH ₃ or another silicon precursor) to form Si-H surface groups such as SiH _x groups on the portion of the surface, thereby forming SiO ₂ -containing The first surface and a second surface containing hydrogen-terminated silicon, such as a -SiH _x surface. A material containing nickel, titanium, iron, or cobalt, such as nickel, nickel nitride (NiN _x ), cobalt, iron, can then be selectively deposited on the first surface (relative to the H-terminated second surface) containing SiO ₂ , Or titanium oxide film.

In some embodiments, the deposition process is a chemical vapor deposition (CVD) type process. In some embodiments, the deposition process is an atomic layer deposition (ALD) type process. In some embodiments, the deposition process is a pure atomic layer deposition process in which each surface reaction is self-limiting. In some embodiments, the deposition process is a vapor deposition process including one or more deposition cycles in which substrates are alternately and sequentially contacted with the first gaseous reactant and the second gaseous reactant.

In certain embodiments, the second surface with respect to H terminated on a substrate (e.g., surface -SiH _x) selectively in a first surface of the same substrate as described above (e.g., a first surface of a substrate of SiO ₂₎ A material containing nickel, such as a nickel layer, is deposited thereon.

In certain embodiments, the second H-terminated surface on the substrate (e.g. -SiH _3, -SiH _2, or -SiH surface) with respect to the first surface of the selectively same substrate as described above (e.g. _{On the} first surface of SiO _{2 of the} substrate), a material containing cobalt, such as a cobalt layer, is deposited.

In certain embodiments, the second H-terminated surface on the substrate (e.g. -SiH _3, -SiH _2, or -SiH surface) with respect to the first surface of the selectively same substrate as described above (e.g. On the substrate (the first surface of SiO ₂ ), a material containing iron, such as an iron layer, is deposited.

In certain embodiments, the second surface with respect to H terminated on a substrate (e.g., containing -SiH _3, -SiH _2, or the surface of -SiH), the first selective surface of the same substrate as described above in A material containing nickel, such as a nickel nitride (NiN _x ) layer, is deposited (eg, the first surface of SiO _{2 of the} substrate).

In certain embodiments, the second surface with respect to H terminated on a substrate (e.g., containing -SiH _3, -SiH _2, or the surface of -SiH), the first selective surface of the same substrate as described above in A material containing titanium, such as a titanium oxide layer, is deposited on (eg, the first surface of SiO _{2 of the} substrate).

In certain embodiments, with respect to the second surface of the substrate H-terminated, such as the first surface (surface of the substrate e.g. SiO ₂₎ is deposited as described herein on a substrate having a selectivity of at least about 90%, at least Selectivity of about 95%, at least about 96%, 97%, 98%, or 99% or more selectivity. In some embodiments, the deposition occurs only on the first surface and not on the second surface. In some embodiments, the deposition on the first surface of the substrate (relative to the second surface of the substrate) has a selectivity of at least about 70% or at least about 80%, which may be sufficient for some Application-specific selectivity. In some embodiments, the deposition on the first surface of the substrate (relative to the second surface of the substrate) has a selectivity of at least about 50%, which may be a selectivity sufficient for certain specific applications.

In certain embodiments, an etch step may be used after deposition or during deposition to remove non-selectively deposited material. Although adding an etching step will generally increase the cost and complexity of the process, in some cases it may be commercially desirable, for example if it is less expensive than other options overall. In some embodiments, the etching process may be a wet etching process or a dry etching process. In some embodiments, dry etching is preferred.

In certain embodiments, with respect to the second surface of the substrate H-capped, as in the first deposited on the surface (e.g., SiO ₂ the first surface of the substrate) of the substrate as described herein may be performed prior to selective loss Up to about 500 deposition cycles, or up to about 50 deposition cycles, or up to about 20 deposition cycles, or up to about 10 deposition cycles, or up to about 5 deposition cycles before the selectivity is lost. In some embodiments, it may be useful to deposit even 1 or 2 cycles before loss of selectivity.

Depending on the specific situation, when the deposition on the first surface of the substrate relative to the second surface of the substrate has less than about 50%, less than about 60%, less than about 70%, less than about 80%, less than about 90% When selectivity, a selectivity of less than about 95%, a selectivity of less than about 96%, 97%, 98%, or 99%, or a selectivity of less than 99%, it is considered that a loss of selectivity has occurred.

In certain embodiments, with respect to a second surface of the substrate H-terminated, deposited on the first surface (e.g., the first surface of the substrate SiO ₂₎ may be performed up to about 50 nm prior to the loss of selectivity Thickness, or up to about 10 nm, or up to about 5 nm, or up to about 3 nm, or up to about 2 nm, or up to about 1 nm before loss of selectivity. In some embodiments, it may be useful to deposit even 3 Angstroms (Å) or 5 Angstroms before loss of selectivity. Depending on the specific situation, when the deposition on the first surface of the substrate (relative to the second surface of the substrate) has a selectivity of less than about 50%, a selectivity of less than about 60%, less than about 70%, and less than about A selectivity of 80%, a selectivity of less than about 90%, a selectivity of less than about 95%, a selectivity of less than about 96%, 97%, 98%, or 99% or a selectivity of less than 99% can be considered to have occurred The loss of selectivity.

Chemical vapor deposition process

In certain embodiments, a chemical vapor deposition may be used with respect to a second surface of H-terminated (e.g., as described herein comprises -SiH _3, -SiH _2, or the surface of -SiH), selectively above depositing on said first substrate surface (e.g. -OH first surface, a _second surface e.g. SiO) comprising nickel, titanium, iron, or cobalt material, e.g., nickel (NiN _x) nitride, cobalt, iron, or Titanium oxide. In some embodiments, a material including nickel, titanium, iron, or cobalt (e.g., nickel, nickel nitride, cobalt, or iron) is selectively deposited by a pulsed chemical vapor deposition process (pulsed CVD process). In a pulsed chemical vapor deposition process, multiple pulses of nickel, nickel nitride, cobalt, or iron precursors or reactants are separated by a purge or removal step in which the reactants are removed from the substrate surface .

Chemical vapor deposition type processes typically involve a gas phase reaction between two or more reactants. Reagents can be provided to the reaction space or substrate at the same time. The substrate or reaction space may be heated to promote the reaction between the gaseous reactants. CVD deposition occurs when reactants are provided to a reaction space or substrate. In certain embodiments, the reactants are provided until a thin film having a desired thickness is deposited. As described above, in certain embodiments, a cyclic chemical vapor deposition type process having multiple cycles for depositing a thin film having a desired thickness may be used. In some embodiments, one or more plasma reactants may be used in a chemical vapor deposition process.

In some embodiments, the atomic layer deposition-process can be modified to a partial chemical vapor deposition process. In some embodiments, a partial chemical vapor deposition process may include at least partially decomposing one or more precursors. In some embodiments, the atomic layer deposition process may be modified to a pulsed chemical vapor deposition process. In some embodiments, the atomic layer deposition process is modified to use pulses of overlapping or partially overlapping reactants. In some embodiments, the atomic layer deposition process is modified to use a very short purge (purge) or removal time, for example less than 0.1 second (depending on the reactor). In some embodiments, the atomic layer deposition process is modified to use extremely long or continuous pulse times. For example, in some embodiments, the atomic layer deposition process is modified to completely eliminate the use of purge or removal after at least one pulse. In some embodiments, no purge is used after the metal reactant pulse. In certain embodiments, no purge is used after the oxygen reactant pulse. In certain embodiments, no purge is used after the metal reactant pulse or the oxygen reactant pulse.

In some embodiments, a single metal precursor is utilized. Therefore, in some embodiments, the process may not include contacting the substrate with the gaseous second reactant. In some embodiments, the substrate is exposed to a precursor pulse, or successive precursor pulses are separated by a precursor removal or purging step. For example, in some embodiments, the substrate may be contacted continuously or intermittently with the gaseous metal precursor but not with the gaseous second reactant. However, in some embodiments, in addition to the vapor-phase metal precursor, the substrate may be contacted with another type that does not react, such as an inert purge gas or a carrier gas. In some embodiments, the deposition process may include only one metal precursor pulse. In some embodiments, the substrate can be brought into contact with a gaseous metal precursor, excess metal precursor and reaction byproducts (if present) can be removed from the substrate surface, and the substrate can be brought into contact with gas again, for example, in a continuous pulse Phase metal precursor. In some embodiments, the substrate may not be contacted with the second reactant. However, in some embodiments, in addition to the vapor-phase metal precursor, the substrate may be contacted with another type that does not react, such as an inert purge gas or a carrier gas.

Atomic layer deposition process

Atomic layer deposition processes are controlled, self-limiting surface reactions based on precursor chemicals. Gas phase reactions are avoided by contacting the substrate with reactants or precursors alternately and sequentially. For example, gas phase reactants are separated from each other on the substrate surface by removing excess reactants and / or reactant by-products from the reaction chamber or the substrate surface between the reactant pulses or by moving the substrate from one reactant. To another reactant.

In short, a substrate including a first surface and a different second surface is typically heated to a suitable deposition temperature under reduced pressure. The deposition temperature is usually kept below the thermal decomposition temperature of the reactants but at a sufficiently high level to avoid condensation of the reactants and provide activation energy for the desired surface reaction. Of course, for any given atomic layer deposition reaction, the appropriate temperature window will depend on the surface capping and reactant species involved.

Here, the temperature is preferably at or below 500 ° C, more preferably at or below 400 ° C, and most preferably from about 100 ° C to about 350 ° C. In some cases, for example, where deposition is performed using a nickel betadiketiminato compound, a temperature from about 275 ° C to about 325 ° C can be selected.

The surface of the substrate may be brought into contact with the gaseous first reactant. The conditions are preferably selected such that only a single layer of the first reactant is adsorbed on the substrate surface in a self-limiting manner. Appropriate contact times can be easily determined by those skilled in the art based on the particular situation.

In some embodiments, excess first reactants and reaction byproducts, if any, are removed from the surface of the substrate, for example, by purging with an inert gas. Purging means For example, gas phase precursors and / or gas phase by-products are removed from the substrate surface by evacuating the chamber with a vacuum pump and / or by replacing the gas in the reactor with an inert gas such as argon or nitrogen. Typical purge times are from about 0.05 seconds to 20 seconds, more preferably between about 1 second and 10 seconds, and still more preferably between about 1 second and 2 seconds. However, other purging times may be used as needed, such as in situations where a high conformal step coverage is needed over extremely high aspect ratio structures or other structures with complex surface morphology. In some embodiments, the substrate is removed from a reaction space containing a first reactant.

The surface of the substrate is brought into contact with the gaseous second gaseous reactant. The surface reaction excess second reactant and gaseous by-products, if present, are removed from the substrate surface. In some embodiments, this can be achieved by purging. In some embodiments, the substrate is removed from a reaction space containing a second reactant.

The steps of contacting and removing are repeated until a thin film of a desired thickness has been selectively formed on the first surface of the substrate, wherein each cycle leaves only a molecular monolayer. Other stages with the operation of alternately and sequentially contacting the surface of the substrate with other different reactants may be included to form more complex materials, such as ternary materials.

Excess reactants or precursors are usually supplied at each stage to saturate the surface of the susceptible structure. Surface saturation ensures that the reactants occupy all available reactive sites (e.g., constrained by physical size or "steric hindrance"), and therefore ensures excellent step coverage. Generally, less than one molecular layer of material is deposited per cycle, however, in some embodiments, more than one molecular layer is deposited during the cycle.

Removing excess reactants or precursors may include evacuating certain contents of the reaction space and / or purging the reaction space with helium, nitrogen, or another inert gas. In some embodiments, purging may include turning off the flow of reactive gas while continuing to flow the inert carrier gas to the reaction space.

The precursor used in the atomic layer deposition process may be a solid, liquid, or gaseous material under standard conditions (room temperature and atmospheric pressure), provided that the precursor is in a gas phase before it contacts the substrate surface. Contacting the substrate surface with the vaporized precursor means that the precursor vapor is in contact with the substrate surface for a limited period of time. Generally, the contact time is about 0.05 to 10 seconds. However, depending on the type of substrate and its surface area, the contact time can be even higher than 10 seconds. In some cases, the contact time may be about several minutes. The optimal exposure time can be determined by those skilled in the art based on the specific situation.

The mass flow rate of the precursor can also be determined by those skilled in the art. In some embodiments, the flow rate of the metal precursor is preferably between about 1 standard milliliter / minute (sccm) and 1000 standard milliliter / minute and is not limited, and more preferably between about 100 standard milliliter / minute and 500 standard Ml / min.

The pressure in the reaction chamber is usually from about 0.01 mbar to about 20 mbar, and more preferably from about 1 mbar to about 10 mbar. However, in some cases, the pressure will be higher or lower than this range, which can be determined by a person skilled in the art in a given context.

Before starting the deposition of the film, the substrate is usually heated to a suitable growth temperature. The growth temperature varies depending on the type of thin film formed, the physical properties of the precursor, and the like. This article discusses growth in more detail for each type of film formed temperature. The growth temperature may be lower than the crystallization temperature of the deposited material to form an amorphous thin film, or the growth temperature may be higher than the crystallization temperature to form a crystalline thin film. The preferred deposition temperature can vary depending on several factors, such as, but not limited to, reactant precursors, pressure, flow rate, reactor arrangement, crystallization temperature of the deposited film, and the composition of the substrate (including the material to be deposited on the substrate). Nature). The specific growth temperature can be selected by those skilled in the art.

Examples of suitable reactors that can be used include the following commercially available equipment: for example, available from ASM America, Inc. of Phoenix, Arizona, and ASM Europe Ltd., Almere, Netherlands. F-120 ^® reactors, F-450 ^® reactors, Pulsar ^® reactors-such as Pulsar ^® 2000 and Pulsar ^® 3000-EmerALD ^® reactors and Advanced ^® 400 series reactor. Other commercial reactor includes a reactor under the trade name of the benefits of high (Eagle ^®) XP and Eagle ^® XP8 from ASM Japan Co., Ltd. (Tokyo, Japan (Tokyo, Japan)) obtained.

In some embodiments, a batch reactor may be used. Suitable batch reactors include, but are not limited to, those commercially available under the trade names ALDA400 ^™ and A412 ^™ from ASM Europe Ltd. (Almere, Netherlands). In some embodiments, a vertical batch reactor, such as A412 ^(TM ), is used in which the boat rotates during processing. Therefore, in some embodiments, the wafer is rotated during processing. In some embodiments where a batch reactor is used, wafer-to-wafer uniformity is less than 3% (1 sigma), less than 2%, less than 1%, or even less than 0.5%.

The growth process may be performed in a reactor or a reaction space connected to a cluster tool as required. In the clustering tool, since each reaction space is dedicated to one type of processing, the temperature of the reaction space in each module can be kept constant, as compared to the case where the substrate is heated to the process temperature before each run The reactor increases throughput.

The stand-alone reactor may be equipped with a load-lock. In this case, it is not necessary to cool the reaction space between each run.

Referring to FIG. 1 and according to some embodiments, a substrate including a first surface (eg, SiO ₂ ) as described above is provided at step 110. A portion of the oxide surface is selectively treated at 120 to form a H-terminated surface. For example, the portion may be for example selective etching of the surface to be formed comprising HF -SiH _3, -SiH _2, or H-terminated surface of -SiH.

With the atomic layer deposition process 100 including multiple cycles, a material including nickel, titanium, iron, or cobalt, such as nickel, is selectively deposited on the first surface of SiO _{2 of the} substrate with respect to the second surface terminated by H. Nickel nitride (NiN _x ), cobalt, iron, or titanium oxide, each cycle includes the following steps.

At step 130, the surface of the substrate is brought into contact with the vaporized first precursor. The first precursor may include a nickel precursor, a cobalt precursor, an iron precursor, or a titanium precursor.

At step 140, excess first precursor and reaction byproducts, if present, are removed from the surface.

At step 150, the surface of the substrate is brought into contact with the vaporized second reactant.

At step 160, the first on the first surface of the substrate is removed from the surface An excess of the second reactant and any gaseous by-products formed in the reaction between the precursor layer and the second reactant.

And, at step 170, the contacting and removing steps are repeated as needed until a thin film including a selectively deposited material having a desired thickness has been formed.

As described above, in some embodiments, one or more surfaces of the substrate may be processed prior to commencing the deposition process 100 to enhance deposition on one surface (as opposed to one or more different surfaces). In FIG. 1, this is indicated by step 120.

Although the illustrated deposition cycle begins with contacting the surface of the substrate with the first precursor, in other embodiments, the deposition cycle begins with contacting the surface of the substrate with the second reactant. Those skilled in the art should understand that, generally, contacting the substrate surface with the first precursor and contacting the substrate surface with the second reactant are interchangeable in the atomic layer deposition cycle.

In some embodiments, the reactants and reaction by-products can be removed from the surface of the substrate by stopping the flow of the first precursor while continuing to flow an inert carrier gas such as nitrogen or argon.

In some embodiments, the reactants and reaction by-products can be removed from the surface of the substrate by stopping the flow of the second reactant while continuing to flow the inert carrier gas. In some embodiments, the substrate is moved such that different reactants contact the surface of the substrate alternately and sequentially in a desired order within a desired time. In some embodiments, removal steps 140 and 160 are not performed. In some embodiments, reactants may not be removed from portions of the chamber. In some embodiments, the substrate is moved from a portion of the chamber containing the first precursor to another portion of the chamber containing the second reactant. In some embodiments During the process, the substrate is moved from the first reaction chamber to a different second reaction chamber.

In some embodiments, each reaction is self-limiting and achieves single layer growth one by one. These can be called "true atomic layer deposition" reactions. In certain such embodiments, a nickel precursor (or other precursor as described herein) may be adsorbed on the substrate surface in a self-limiting manner. The second reactant will then react with the adsorbed nickel precursor to form a single layer of nickel (or other material as described herein) on the substrate.

However, in certain embodiments, an atomic layer deposition type reaction is provided in which there may be a certain precursor that decomposes but saturates growth. That is, in some embodiments, although a certain amount of film growth can be caused by thermal decomposition of a nickel precursor (or other metal precursor as described herein) at certain deposition temperatures, the Saturated growth is preferably achieved with two reactants. Such a reaction is an example of an atomic layer deposition type reaction. In such an atomic layer deposition type reaction, a film with good uniformity and relatively few impurities can be deposited.

In certain embodiments, thermal decomposition of one or more precursors occurs, especially nickel, cobalt, iron, or titanium precursors. In this case, the growth rate may not be completely stable with increasing pulse time. In contrast, the growth rate may continue to increase with increasing pulse time, but the growth rate may increase more slowly with increasing pulse time. Therefore, in some embodiments, a pulsed chemical vapor deposition type deposition process is used in which reactants are provided alternately and separately but certain gas phase reactions can occur. The conditions are preferably selected such that the mechanism of the decomposition is surface controlled decomposition, which results in good uniformity and good step coverage. The reaction conditions can also be selected as Maintain good control of the reaction so that a good quality film with low impurities is produced.

Thus, in some embodiments, the deposition temperature is lower than the thermal decomposition temperature of the nickel precursor (or other precursors as described herein), while in other embodiments, the deposition temperature may be at or above the thermal decomposition temperature Decomposition temperature.

As described above, in some embodiments, the H-terminated second surface (for example, -SiH ₃ , -SiH ₂ , or -SiH capped surface) is selectively processed by a pulsed chemical vapor deposition process. A thin film is deposited on a first surface, such as a SiO ₂ surface, in which a gas-phase metal precursor is intermittently pulsed into a reaction space including a substrate and purged from the reaction space. In some embodiments, a single metal precursor is utilized. In some embodiments, the substrate is exposed to a precursor pulse, or a continuous precursor pulse separated by a precursor removal or purge step. Therefore, in some embodiments, the process may not include contacting the substrate with the gaseous second reactant. For example, in some embodiments, the substrate may be contacted continuously or intermittently with the gaseous metal precursor and without contacting the gaseous second reactant. However, in some embodiments, in addition to the vapor-phase metal precursor, the substrate may be contacted with another type that does not react, such as an inert purge gas or a carrier gas. In some embodiments, the deposition process may include only one metal precursor pulse. In some embodiments, the substrate can be brought into contact with the gaseous metal precursor, excess metal precursor and reaction byproducts (if present) can be removed from the substrate surface, and the substrate can be brought into contact with gas again, for example, in a continuous pulse Phase metal precursor. In some embodiments, the substrate may not be contacted with the second reactant. However, in some embodiments, in addition to the vapor-phase metal precursor, the substrate may be contacted with another type that does not react, such as an inert purge gas or a carrier gas.

Selectively in SiO ₂ Deposited nickel

As described above, in certain embodiments, the H-terminated second surface of the substrate (eg, -SiH ₃ , -SiH ₂ , or -SiH surface) is selectively on the surface of the first substrate (as described above, For example, a material containing nickel is deposited on the surface of SiO _{2 of the} same substrate.

In some embodiments, the H-capped second surface is formed before deposition by processing the surface to provide H-capped, and thereby suppressing nickel deposition on the second surface (as opposed to the first surface). In some embodiments, the processing may be an in situ processing. In some embodiments, the second surface may be a SiO ₂ surface that is treated to provide an H-terminated surface (eg, -SiH ₃ , -SiH ₂ , or -SiH-terminated surface). In certain embodiments, chemicals can make contact with the second surface, said capping chemical to provide H (e.g., by forming -SiH _3, -SiH _2, or -SiH surface). In some embodiments, the treatment of the SiO ₂ surface may include etching the surface with HF (eg, 0.5% HF). Masks or other processes may be used to process one or more portions of the first surface to form an H-capped second surface. For example, a mask or other process may be used to selectively etch one or more portions of the SiO ₂ surface to form a second SiH _x surface while keeping the remaining portion of the first surface of SiO ₂ undisturbed.

In some embodiments, the first surface may be treated to enhance nickel deposition on the first surface. For example, the first surface of SiO ₂ may be treated to increase the amount of OH groups on the surface.

In certain embodiments, a second surface, the first surface (e.g. SiO ₂ with respect to the first surface of the substrate SiH _x of the second substrate surface) on a nickel deposit having at least about 90% selectivity, Selectivity of at least about 95%, at least about 96%, 97%, 98%, or 99% or more selectivity. In some embodiments, the deposition occurs only on the first surface and not on the second surface. In some embodiments, the deposition on the first surface of the substrate (relative to the second surface of the substrate) has a selectivity of at least about 50%, a selectivity of at least about 70%, or a selectivity of at least about 80% This may be sufficient selectivity for some specific applications.

Referring to FIG. 2 and according to some embodiments, a substrate including a first surface (eg, a SiO ₂ surface) as described above is provided at step 210. A portion of the SiO ₂ surface is selectively processed by exposure to HF at step 220 to form a H-terminated second surface (eg, -SiH ₃ , -SiH ₂ , or -SiH surface).

The SiO ₂ surface by vapor deposition process (e.g., by atomic layer deposition or chemical vapor deposition) selectively in the substrate at step 230 (with respect to the surface of the capping H) deposited on a material comprising nickel.

In some embodiments, the SiO ₂ first surface of the substrate in the reaction chamber (relative to the H-terminated second surface (e.g., -SiH) is selectively formed by an atomic layer deposition type process including multiple nickel deposition cycles. _3, -SiH _2, or -SiH surface) is formed on the nickel thin film element), each deposition cycle comprising: contacting a substrate surface comprising a first gas phase reactor was first nickel precursor to form a nickel layer on a substrate precursor Removing excess first reactant from the surface of the substrate; contacting the substrate with a second gaseous reactant such that the second reactant reacts with the first nickel precursor on the substrate in a self-limiting manner to form nickel; and Excessive second reactants and reaction byproducts, if present, are removed from the substrate surface.

This may be referred to as a nickel deposition cycle. Each nickel deposition cycle typically selectively forms up to about one nickel monolayer on the SiO ₂ surface. In some cases where the deposition temperature is higher than the decomposition temperature of the nickel precursor, more than one nickel monolayer may be formed in each nickel deposition cycle. The nickel deposition cycle can be repeated until a film of the desired thickness is formed.

Although the nickel deposition cycle shown begins with providing a first nickel precursor, in other embodiments, the deposition cycle begins with providing a second reactant. Those skilled in the art will understand that providing a first nickel precursor and providing a second reactant are interchangeable in an atomic layer deposition cycle.

In some embodiments, the reactants and reaction by-products can be removed from the substrate surface by stopping the flow of the reactants while continuing to flow an inert carrier gas such as nitrogen or argon. In some embodiments, the reactants and reaction byproducts can be removed from the surface of the substrate by removing the substrate from the reaction chamber or moving the substrate within the reaction chamber.

As described above, in some embodiments, the H-terminated second surface (for example, -SiH ₃ , -SiH ₂ , or -SiH capped surface) is selectively A nickel film is deposited on a first surface (such as a SiO ₂ surface), wherein a gas phase nickel precursor is alternately pulsed into a reaction space including a substrate and purged from the reaction space.

In some embodiments, a single nickel precursor is utilized. Therefore, in some embodiments, the process may not include contacting the substrate with the gaseous second reactant. In some embodiments, the substrate is exposed to one precursor pulse, or a continuous precursor pulse separated by a precursor removal or purging step. For example, in some embodiments, the substrate can be continuously or intermittently contacted with the vapor-phase nickel precursor and not contacted with the vapor-phase second reactant. However, in some embodiments, in addition to the vapor phase nickel precursor, the substrate can be contacted Another type that does not react, such as an inert purge gas or a carrier gas. In some embodiments, the deposition process may include only one nickel precursor pulse. In some embodiments, the substrate can be brought into contact with the gas phase nickel precursor, excess nickel precursor and reaction byproducts (if present) can be removed from the substrate surface, and the substrate can be brought into contact with gas again, for example, in a continuous pulse Phase nickel precursor. In some embodiments, the substrate may not be contacted with the second reactant. However, in some embodiments, in addition to the vapor phase nickel precursor, the substrate may be contacted with another type that does not react, such as an inert purge gas or a carrier gas.

Selectively in SiO ₂ NiN _x

As described above, in certain embodiments, the second surface of the substrate H-terminated (e.g. -SiH _3, -SiH _2, or -SiH surface) with respect to the first surface of the substrate selectively as described above ( For example, a material including nickel, such as a material including nickel nitride (NiN _x ), is deposited on the first surface of SiO _{2 on the} same substrate.

In some embodiments, the H-capped second surface is formed before deposition by processing the surface to provide H-capped, and thereby suppressing the deposition of nickel-containing on the second surface (relative to the first surface). Material (such as nickel nitride). In some embodiments, the processing may be an in-situ processing. In some embodiments, the second surface may be a SiO ₂ surface that is treated to provide an H-terminated surface (eg, -SiH ₃ , -SiH _2, or -SiH-terminated surface). In certain embodiments, chemicals can make contact with the second surface, said capping chemical to provide H (e.g., by forming -SiH _3, -SiH ₂ -SiH or surface). In some embodiments, the treatment of the SiO ₂ surface may include etching the surface with HF (eg, 0.5% HF). Masks or other processes may be used to process one or more portions of the first surface to form an H-capped second surface. For example, a mask or other process may be used to selectively etch one or more portions of the SiO ₂ surface to form a SiH _x second surface while keeping the remainder of the SiO ₂ first surface undisturbed.

In some embodiments, the first surface may be treated to enhance the deposition of a material comprising nickel (eg, nickel nitride) on the first surface. For example, the first surface of SiO ₂ may be treated to increase the amount of OH groups on the surface.

In some embodiments, the NiN _x deposition on the first surface (eg, the first SiO ₂ surface of the substrate) relative to the H-terminated second surface of the substrate has a selectivity of at least about 90%, at least about 95% Selectivity of at least about 96%, 97%, 98%, or 99% or more. In some embodiments, NiN _x deposition occurs only on the first surface and not on the second surface. In certain embodiments, NiN _x deposited on the first surface of the substrate (relative to the second surface of the substrate) having at least about 50% selectivity, selectivity of at least about 70%, or at least about 80% Selectivity, which may be sufficient for some specific applications.

Referring to FIG. 3 and according to some embodiments, at step 310, a substrate including a surface (such as a SiO ₂ surface) as described above is provided. A portion of the SiO ₂ surface is selectively processed by exposure to HF at step 320 to form a second surface including H-terminated (eg, -SiH ₃ , -SiH ₂ , or -SiH).

A material containing nickel, such as nickel nitride, is selectively deposited on the SiO ₂ surface of the substrate with respect to the H-terminated surface by a vapor deposition process (such as by atomic layer deposition or chemical vapor deposition) at step 330. (NiN _x ).

In some embodiments, the SiO ₂ first surface (relative to the H-terminated second surface) is selectively on the substrate in the reaction chamber by an atomic layer deposition type process including multiple nickel nitride deposition cycles. For example, SiH _x capped surface)) is used to form a material containing nickel, such as a nickel nitride film, and each deposition cycle includes: contacting the substrate surface with a first gas-phase reactant including a first nickel precursor to form nickel on the substrate Precursor layer; removing excess first reactant from the substrate surface; contacting the substrate with a second gas phase nitrogen reactant so that the second reactant reacts with the first nickel precursor on the substrate in a self-limiting manner to form a material containing nickel, for example NiN _x; and removing excess second reactant and reaction byproducts (if present) from the substrate surface.

This may be referred to as a NiN _x deposition cycle. Each NiN _x deposition cycle typically selectively forms up to about one NiN _x monolayer on the SiO ₂ surface. In some cases, the deposition temperature is higher than the decomposition temperature of the nickel precursor, may form more than a monolayer NiN _x NiN _x in each deposition cycle. The NiN _x deposition cycle is repeated until a film of the desired thickness is formed.

In some embodiments, the reactants and reaction by-products can be removed from the substrate surface by stopping the flow of the reactants while continuing to flow an inert carrier gas such as nitrogen or argon. In some embodiments, the reactants and reaction byproducts can be removed from the surface of the substrate by removing the substrate from the reaction chamber or moving the substrate within the reaction chamber.

As described above, in some embodiments, by means of a chemical vapor deposition process (such as a pulsed chemical vapor deposition process) in which a nickel precursor and a nitrogen precursor are provided to a reaction chamber, The two surfaces selectively deposit a NiN _x layer on the first surface (such as the SiO ₂ surface of the substrate) as described above.

In some embodiments, a single nickel precursor is utilized. Therefore, in some embodiments, the process may not include contacting the substrate with the gaseous second reactant. In some implementations In an example, the substrate is exposed to a precursor pulse, or a continuous precursor pulse separated by a precursor removal or purging step. For example, in some embodiments, the substrate can be continuously or intermittently contacted with the vapor-phase nickel precursor and not contacted with the vapor-phase second reactant. However, in some embodiments, in addition to the vapor phase nickel precursor, the substrate may be contacted with another type that does not react, such as an inert purge gas or a carrier gas. In some embodiments, the deposition process may include only one nickel precursor pulse. In some embodiments, the substrate can be brought into contact with the gas phase nickel precursor, excess nickel precursor and reaction byproducts (if present) can be removed from the substrate surface, and the substrate can be brought into contact with gas again, for example, in a continuous pulse Phase nickel precursor. In some embodiments, the substrate may not be contacted with the second reactant. However, in some embodiments, in addition to the vapor phase nickel precursor, the substrate may be contacted with another type that does not react, such as an inert purge gas or a carrier gas.

Selectively in SiO ₂ Deposited cobalt

As described above, in certain embodiments, the H-terminated second surface of the substrate (eg, -SiH ₃ , -SiH ₂ , or -SiH surface) is selectively on the surface of the first substrate (as described above, For example, a material containing cobalt is deposited on the surface of SiO _{2 of the} same substrate.

In some embodiments, the H-capped second surface is formed prior to deposition by treating the surface to provide H-capped, and thereby suppress cobalt deposition on the second surface (as opposed to the first surface). In some embodiments, the processing may be an in-situ processing. In some embodiments, the second surface may be a SiO ₂ surface that is treated to provide an H-terminated surface (eg, -SiH ₃ , -SiH ₂ , or -SiH-terminated surface). In certain embodiments, chemicals can make contact with the second surface, said capping chemical to provide H (e.g., by forming -SiH _3, -SiH _2, or -SiH surface). In some embodiments, the treatment of the SiO ₂ surface may include etching the surface with HF (eg, 0.5% HF). Masks or other processes may be used to process one or more portions of the first surface to form an H-capped second surface. For example, a mask or other process may be used to selectively etch one or more portions of the SiO ₂ surface to form a SiH _x second surface while keeping the remainder of the SiO ₂ first surface undisturbed.

In some embodiments, the first surface may be treated to enhance cobalt deposition on the first surface. For example, the first surface of SiO ₂ may be treated to increase the amount of OH groups on the surface.

In certain embodiments, the first surface with respect to the second surface (e.g. SiO ₂ SiH _x first surface of the substrate with respect to the second surface of the substrate) is deposited on cobalt at least about 90% selectivity, Selectivity of at least about 95%, at least about 96%, 97%, 98%, or 99% or more selectivity. In some embodiments, the deposition occurs only on the first surface and not on the second surface. In some embodiments, the deposition on the first surface of the substrate (relative to the second surface of the substrate) has a selectivity of at least about 50%, a selectivity of at least about 70%, or a selectivity of at least about 80% This may be sufficient selectivity for some specific applications.

Referring to FIG. 4 and according to some embodiments, at step 410, a substrate including a first surface (eg, a SiO ₂ surface) as described above is provided. A portion of the SiO ₂ surface is selectively processed at step 420 to form an H-terminated second surface (eg, -SiH ₃ , -SiH ₂ , or -SiH surface) by exposure to HF.

At step 430 by vapor deposition process (e.g., by atomic layer deposition or chemical vapor deposition) with respect to the surface of H-terminated cobalt selectively deposited on surface of the SiO ₂ substrate.

In some embodiments, the SiO ₂ first surface (relative to the H-terminated second surface (-SiH ₃ , -SiH ₂ , or -SiH capped surface)) to form an elemental cobalt film, each deposition cycle includes: contacting the substrate surface with a first gas-phase reactant containing a first cobalt precursor to form a cobalt precursor on the substrate Removing excess first reactant from the surface of the substrate; contacting the substrate with the second gaseous reactant such that the second reactant reacts with the first cobalt precursor on the substrate in a self-limiting manner to form cobalt; and Excessive second reactants and reaction byproducts, if present, are removed from the substrate surface.

This may be referred to as a cobalt deposition cycle. Each cobalt deposition cycle typically selectively forms up to about one cobalt monolayer on the SiO ₂ surface. In some cases where the deposition temperature is higher than the decomposition temperature of the cobalt precursor, more than one cobalt monolayer may be formed in each cobalt deposition cycle. The cobalt deposition cycle is repeated until a film of the desired thickness is formed.

Although the cobalt deposition cycle shown begins with providing a first cobalt precursor, in other embodiments, the deposition cycle begins with providing a second reactant. Those skilled in the art will understand that providing a first cobalt precursor and providing a second reactant are interchangeable in an atomic layer deposition cycle.

In some embodiments, the reactants and reaction by-products can be removed from the substrate surface by stopping the flow of the reactants while continuing to flow an inert carrier gas such as nitrogen or argon. In some embodiments, the reactants and reaction byproducts can be removed from the surface of the substrate by removing the substrate from the reaction chamber or moving the substrate within the reaction chamber.

As described above, in some embodiments, the H-terminated surface (e.g. -SiH ₃ , -SiH ₂ , or -SiH capped surface) selectively deposits a cobalt film on a first surface (eg, a SiO ₂ surface).

In some embodiments, a single cobalt precursor is utilized. Therefore, in some embodiments, the process may not include contacting the substrate with the gaseous second reactant. In some embodiments, the substrate is exposed to one precursor pulse, or a continuous precursor pulse separated by a precursor removal or purging step. For example, in some embodiments, the substrate may be contacted continuously or intermittently with the gas-phase cobalt precursor and without contacting the gas-phase second reactant. However, in some embodiments, in addition to the vapor-phase cobalt precursor, the substrate may be contacted with another type that does not react, such as an inert purge gas or a carrier gas. In some embodiments, the deposition process may include only one cobalt precursor pulse. In some embodiments, the substrate can be brought into contact with the gas phase cobalt precursor, excess cobalt precursor and reaction byproducts (if present) can be removed from the substrate surface, and the substrate can be brought into contact with the gas again, for example, in successive pulses Phase cobalt precursor. In some embodiments, the substrate may not be contacted with the second reactant. However, in some embodiments, in addition to the vapor-phase cobalt precursor, the substrate may be contacted with another type that does not react, such as an inert purge gas or a carrier gas.

Selectively in SiO ₂ Deposited iron

As described above, in certain embodiments, the H-terminated second surface of the substrate (eg, -SiH ₃ , -SiH ₂ , or -SiH surface) is selectively on the surface of the first substrate (as described above, For example, a material containing iron is deposited on the SiO ₂ surface of the same substrate.

In some embodiments, the H-capped second surface is formed prior to deposition by treating the surface to provide H-capped, and thereby suppress iron deposition on the second surface (as opposed to the first surface). In some embodiments, the processing may be an in-situ processing. In some embodiments, the second surface may be a SiO ₂ surface that is treated to provide an H-terminated surface (eg, -SiH ₃ , -SiH ₂ , or -SiH surface). In certain embodiments, chemicals can make contact with the second surface, said capping chemical to provide H (e.g., by forming -SiH _3, -SiH ₂ -SiH or surface). In some embodiments, the treatment of the SiO ₂ surface may include etching the surface with HF (eg, 0.5% HF). Masks or other processes may be used to process one or more portions of the first surface to form an H-capped second surface. For example, a mask or other process may be used to selectively etch one or more portions of the SiO ₂ surface to form a SiH _x second surface while keeping the remainder of the SiO ₂ first surface undisturbed.

In some embodiments, the first surface may be treated to enhance iron deposition on the first surface. For example, the first surface of SiO ₂ may be treated to increase the amount of OH groups on the surface.

In some embodiments, the iron deposition on the first surface (eg, the SiO ₂ first surface of the substrate relative to the SiH _x second surface of the substrate) relative to the second surface has a selectivity of at least about 90%, Selectivity of at least about 95%, at least about 96%, 97%, 98%, or 99% or more selectivity. In some embodiments, the deposition occurs only on the first surface and not on the second surface. In some embodiments, the deposition on the first surface of the substrate (relative to the second surface of the substrate) has a selectivity of at least about 50%, a selectivity of at least about 70%, or a selectivity of at least about 80% This may be sufficient selectivity for some specific applications.

Referring to FIG. 5 and according to some embodiments, at step 510, a substrate including a first surface (eg, a SiO ₂ surface) as described above is provided. A portion of the SiO ₂ surface is selectively processed by exposure to HF at step 520 to form an H-terminated second surface (eg, -SiH ₃ , -SiH ₂ , or -SiH surface).

Iron is selectively deposited on the SiO ₂ surface of the substrate with respect to the H-terminated surface by a vapor deposition process (eg, by atomic layer deposition or chemical vapor deposition) at step 530.

In some embodiments, the SiO ₂ first surface (relative to the H-terminated second surface (e.g. -SiH) of the substrate in the reaction chamber is selectively ₃ , -SiH ₂ , or -SiH surface)) forming an elemental iron thin film, each deposition cycle includes: contacting the substrate surface with a first gaseous reactant containing a first iron precursor to form an iron precursor layer on the substrate Removing excess first reactant from the substrate surface; contacting the substrate with the second gaseous reactant such that the second reactant contacts the first iron precursor on the substrate in a self-limiting manner to form iron; and from the substrate The surface removes excess second reactants and reaction byproducts, if present.

This may be referred to as an iron deposition cycle. Each iron deposition cycle typically selectively forms up to about one iron monolayer on the SiO ₂ surface. In some cases where the deposition temperature is higher than the decomposition temperature of the iron precursor, more than one iron monolayer may be formed in each iron deposition cycle. The iron deposition cycle is repeated until a film of the desired thickness is formed.

Although the iron deposition cycle shown begins with providing a first iron precursor, in other embodiments, the deposition cycle begins with providing a second reactant. Skilled in this technology It should be understood that providing a first iron precursor and providing a second reactant are interchangeable in an atomic layer deposition cycle.

In some embodiments, the reactants and reaction by-products can be removed from the substrate surface by stopping the flow of the reactants while continuing to flow an inert carrier gas such as nitrogen or argon. In some embodiments, the reactants and reaction byproducts can be removed from the surface of the substrate by removing the substrate from the reaction chamber or moving the substrate within the reaction chamber.

As described above, in some embodiments, compared with H, a pulsed chemical vapor deposition process in which gas phase iron precursor pulses are alternately provided into a reaction space including a substrate and purged from the reaction space is performed. terminated surface (e.g. -SiH _3, -SiH _2, or -SiH) iron film selectively deposited on the first surface (e.g. SiO ₂ surface).

In some embodiments, a single iron precursor is utilized. Therefore, in some embodiments, the process may not include contacting the substrate with the gaseous second reactant. In some embodiments, the substrate is exposed to a precursor pulse, or a continuous precursor pulse separated by a precursor removal or purge step. For example, in some embodiments, the substrate may be contacted continuously or intermittently with the gas phase iron precursor and without contacting the gas phase second reactant. However, in some embodiments, in addition to the gas phase iron precursor, the substrate may be contacted with another type that does not react, such as an inert purge gas or a carrier gas. In some embodiments, the deposition process may include only one iron precursor pulse. In some embodiments, the substrate can be brought into contact with the gas phase iron precursor, excess iron precursor and reaction by-products (if present) can be removed from the surface of the substrate, and the substrate can be brought into contact with gas again, for example, in successive pulses Phase iron precursor. In some embodiments, the substrate may not be contacted with the second reactant. However, in some embodiments, in addition to the gas phase iron precursor, the substrate can be made Contact another type that does not react, such as an inert purge gas or a carrier gas.

Selectively in SiO ₂ Deposited TiO ₂

As described above, in some embodiments, the titanium-containing layer is selectively deposited on the first substrate surface (such as the first surface of SiO _{2 of the} same substrate) as described above with respect to the H-terminated second surface of the substrate. Materials such as TiO ₂ .

In some embodiments, the H-capped second surface is formed before deposition by treating the surface to provide H-capped, and thereby suppressing the deposition of titanium-containing on the second surface (relative to the first surface). Materials (such as titanium oxide deposition). In some embodiments, the processing may be an in-situ processing. In some embodiments, the second surface may be a SiO ₂ surface that is treated to provide an H-terminated surface (eg, -SiH ₃ , -SiH ₂ , or -SiH surface). In certain embodiments, chemicals can make contact with the second surface, said capping chemical to provide H (e.g., by forming -SiH _3, -SiH ₂ -SiH or surface). In some embodiments, the treatment of the SiO ₂ surface may include etching the surface with HF (eg, 0.5% HF). Masks or other processes may be used to process one or more portions of the first surface to form an H-capped second surface. For example, a mask or other process may be used to selectively etch one or more portions of the SiO ₂ surface to form a -SiH ₃ , -SiH ₂ , or -SiH second surface while maintaining the first surface of the SiO ₂ The rest is not disturbed.

In certain embodiments, the SiO ₂ surface can be treated to increase the amount of OH groups on the surface.

In some embodiments, a titanium-containing layer is deposited on the first surface (eg, the SiO ₂ surface of the substrate) relative to the H-terminated second surface (eg, the -SiH ₃ , -SiH ₂ , or -SiH surface of the substrate) material (e.g., TiO ₂₎ having a selectivity of at least about 90%, at least about 95% selectivity, at least about 96%, 97%, 98%, or 99%, or more than 99% selectivity. In certain embodiments, TiO ₂ deposition occurs only on the first surface and not on the second surface. In certain embodiments, the TiO ₂ deposition on the first surface of the substrate (relative to the second surface of the substrate) has a selectivity of at least about 50%, a selectivity of at least about 70%, or at least about 80%. Selectivity, which may be sufficient for some specific applications.

Referring to FIG. 6 and according to some embodiments, at step 610, a substrate including a SiO ₂ surface is provided. A portion of the SiO ₂ surface is selectively processed by exposure to HF at step 620 to form a H-terminated SiH _x surface.

Titanium oxide is selectively deposited on the SiO ₂ surface of the substrate with respect to the H-terminated surface by a vapor deposition process (eg, by atomic layer deposition or chemical vapor deposition) at step 630.

In some embodiments, a SiO ₂ first surface (relative to an H-terminated second surface (e.g., H SiH _x surface)) forming a material containing titanium, such as a titanium oxide film, each deposition cycle includes: contacting the substrate surface with a first gas phase reactant containing a first titanium precursor to form a titanium precursor layer on the substrate Removing excess first reactant from the substrate surface; contacting the substrate with the second gas phase oxygen reactant so that the second reactant reacts with the first titanium precursor on the substrate in a self-limiting manner to form TiO ₂ ; And removing excess second reactants and reaction byproducts (if present) from the substrate surface.

This may be referred to as the TiO ₂ deposition cycle. Each TiO ₂ deposition cycle typically selectively forms up to about one TiO ₂ monolayer on the SiO ₂ surface. In some cases where the deposition temperature is higher than the decomposition temperature of the titanium precursor, more than one TiO ₂ monolayer may be formed in each TiO ₂ deposition cycle. The TiO ₂ deposition cycle is repeated until a film of the desired thickness is formed.

Although the TiO ₂ deposition cycle shown begins with providing a first titanium precursor, in other embodiments, the deposition cycle begins with providing a second reactant. Those skilled in the art will understand that providing a first titanium precursor and providing a second reactant are interchangeable in an atomic layer deposition cycle.

In some embodiments, the reactants and reaction by-products can be removed from the substrate surface by stopping the flow of the reactants while continuing to flow an inert carrier gas such as nitrogen or argon. In some embodiments, the reactants and reaction byproducts can be removed from the surface of the substrate by removing the substrate from the reaction chamber or moving the substrate within the reaction chamber.

As described above, in some embodiments, by a chemical vapor deposition process (such as a pulsed chemical vapor deposition process) in which a titanium precursor and an oxygen precursor are provided to a reaction chamber, the A TiO ₂ layer is deposited on a first surface of SiO ₂ (relative to the second surface terminated by H). In some embodiments, a single titanium precursor is utilized. Therefore, in some embodiments, the process may not include contacting the substrate with the gaseous second reactant. In some embodiments, the substrate is exposed to a precursor pulse, or a continuous precursor pulse is separated by a precursor removal or purge step. For example, in some embodiments, the substrate may be continuously or intermittently contacted with the vapor-phase titanium precursor and not contacted with the vapor-phase second reactant. However, in some embodiments, in addition to the vapor-phase titanium precursor, the substrate may be contacted with another type that does not react, such as an inert purge gas or a carrier gas. In some embodiments, the deposition process may include only one titanium precursor pulse. In some embodiments, the substrate can be brought into contact with the gas phase titanium precursor, excess titanium precursor and reaction byproducts (if present) can be removed from the surface of the substrate, and the substrate can be brought into contact with gas again, such as in successive pulses Phase titanium precursor. In some embodiments, the substrate may not be contacted with the second reactant. However, in some embodiments, in addition to the vapor-phase titanium precursor, the substrate may be contacted with another type that does not react, such as an inert purge gas or a carrier gas.

Precursor

Suitable nickel precursors can be selected by those skilled in the art. Generally, a nickel compound in which a metal is bound or coordinated with oxygen, nitrogen, carbon, or a combination thereof is preferred. In some embodiments, the nickel precursor may be an organic compound. In some embodiments, the nickel precursor is a metal organic compound. In some embodiments, the nickel precursor is a metal organic compound comprising a bidentate ligand. In certain embodiments, the nickel precursor is bis (4-N-ethylamino-3-pentene-2-N-ethylimino) nickel (ii) (bis (4-N-ethylamino- 3-penten-2-N-ethyliminato) nickel (ii)).

In some embodiments, the nickel precursor may be selected from the group consisting of: a beta betadiketonate compound, a beta betadiketiminato compound, a nickel aminoalkoxide ) Compounds, nickel amidinate compounds, nickel cyclopentadienyl compounds, nickel carbonyl compounds, and combinations thereof. In certain embodiments, X (acac) _y or X (thd) _y compounds are used, where X is a metal, y is usually (but not necessarily) between 2 and 3, and thd is 2,2,6, 6-tetramethyl-3,5-heptanedionate (2,2,6,6-tetramethyl-3,5-heptanedionato). Some examples of suitable β-diimide (eg, Ni (pda) ₂ ) compounds are mentioned in US Patent No. 9,103,019, the disclosure of which is incorporated herein in its entirety. Some examples of suitable fluorenyl compounds (eg, Ni ( ⁱ Pr-AMD) ₂ ) are mentioned in US Patent No. 7,557,229, the disclosure of which is incorporated herein in its entirety.

The nickel precursor may also include one or more halide ligands. In a preferred embodiment, the precursor is a β-diimine nickel compound, such as bis (4-N-ethylamino-3-pentene-2-N-ethylimine) nickel (II) [Ni (EtN-EtN-pent) ₂ ]; nickel ketimine, such as bis (3Z) -4-n-butylamino-pent-3-en-2-one-nickel (II) (bis (3Z) -4-nbutylamino-pent-3-en-2-one-nickel (II)); fluorenyl nickel compounds such as methylcyclopentadienyl-isopropylacetic acid fluorenyl-nickel (II) (methylcyclopentadienyl-isopropylacetamidinate) -nickel (II)); β-diketone nickel compounds such as Ni (acac) ₂ , Ni (thd) ₂ ; or cyclopentadiene nickel compounds such as Ni (cp) ₂ , Ni (Mecp) ₂ , Ni ( Etcp) ₂ or a derivative thereof, such as methylcyclopentadienyl-isopropylacetamidinate-nickel (II). In a more preferred embodiment, the precursor is bis (4-N-ethylamino-3-pentene-2-N-ethylimino) nickel (II) (bis (4-N-ethylamino-3 -penten-2-N-ethyliminato) nickel (II)).

In some embodiments, the first nickel precursor is bis (4-N-ethylamino-3-pentene-2-N-ethylimino) nickel (II) (bis (4-N- ethylamino-3-penten-2-N-ethyliminato) nickel (II)).

Titanium precursors can be selected by those skilled in the art and can be, for example, titanium alkoxides (methoxides, ethoxides, isopropoxides) and titanium alkylmines.

Iron precursors can be selected by those skilled in the art. In certain embodiments, the iron precursor is Cp ₂ Fe or a derivative thereof. In some embodiments, the iron precursor is Fe (acac) ₂ . In some embodiments, the iron precursor is a ferric alkoxide, such as third iron (III) butoxide (Fe ₂ (O ^t Bu) ₆ ). In some embodiments, the iron precursor is iron pentacarbonyl (Fe (CO) ₅ ). In certain embodiments, the iron precursor comprises at least one cyclopentadienyl ligand (Cp), a substituted cyclopentadienyl ligand, or a derivative thereof. In certain embodiments, the iron precursor comprises at least one carbonyl ligand (-CO) or a derivative thereof. In certain embodiments, the iron precursor comprises at least one carbonyl ligand (-CO) and at least one organic ligand (e.g., cyclopentadienyl ligand (Cp) or substituted cyclopentadienyl Ligand) or a derivative thereof.

Cobalt precursors can be selected by those skilled in the art. In certain embodiments, the cobalt precursor may comprise a beta-diketiminato compound, a cobalt ketoiminate compound, a cobalt amidinate compound, or a beta-diketim cobalt compound betadiketonate) compound.

In some embodiments, the second precursor or the second reactant in the atomic layer deposition process for forming elemental nickel is selected from hydrogen and synthesis gas. In other embodiments, the second reactant may be an alcohol, such as ethanol (EtOH).

In some embodiments, the second reactant is an organic reducing agent. The organic reducing agent preferably has a substance selected from the group consisting of an alcohol (-OH) or an aldehyde (-CHO) or a carboxylic acid as described above. At least one functional group in the group consisting of (-COOH).

The reducing agent containing at least one alcohol group may be selected from the group consisting of primary alcohol, secondary alcohol, tertiary alcohol, polyhydric alcohol, cyclic alcohol, aromatic alcohol, halogenated alcohol, and other derivatives of alcohol.

Preferred primary alcohols have an -OH group attached to a carbon atom bonded to another carbon atom, especially a primary alcohol according to formula (I): R ¹ -OH (I)

Wherein R ¹ is a linear or branched C ₁ -C ₂₀ alkyl or alkenyl group, preferably methyl, ethyl, propyl, butyl, pentyl or hexyl. Examples of preferred primary alcohols include methanol, ethanol, propanol, butanol, 2-methylpropanol, and 2-methylbutanol.

Preferred secondary alcohols have an -OH group attached to a carbon atom bonded to two other carbon atoms. Specifically, preferred secondary alcohols have the general formula (II):

Each of R ^{1 is} independently selected from the group of linear or branched C ₁ -C ₂₀ alkyl and alkenyl, preferably methyl, ethyl, propyl, butyl, pentyl, or hexyl. Examples of preferred secondary alcohols include 2-propanol and 2-butanol.

A preferred tertiary alcohol has an -OH group attached to a carbon atom bonded to three other carbon atoms. Specifically, preferred tertiary alcohols have the general formula (III):

Each of R ^{1 is} independently selected from the group of linear or branched C ₁ -C ₂₀ alkyl and alkenyl, preferably methyl, ethyl, propyl, butyl, pentyl, or hexyl. An example of a preferred tertiary alcohol is tertiary butanol.

Preferred polyhydric alcohols (eg, diols and triols) have primary, secondary, and / or tertiary alcohol groups as described above. Examples of preferred polyhydric alcohols are ethylene glycol and glycerol.

A preferred cyclic alcohol has an -OH group attached to at least one carbon atom as part of a ring of 1 to 10 carbon atoms, more preferably 5 to 6 carbon atoms.

Preferred aromatic alcohols have at least one -OH group attached to a benzene ring or a carbon atom in a side chain. Examples of preferred aromatic alcohols include benzyl alcohol, o-cresol, p-cresol, m-cresol and resorcinol.

Preferred halogenated alcohols have the general formula (IV): CH _n X _3-n -R ² -OH (IV)

Where X is selected from the group consisting of fluorine, chlorine, bromine and iodine, n is an integer from 0 to 2, and R ^{2 is} selected from linear or branched C ₁ -C ₂₀ alkyl and alkenyl, preferably methyl , Ethyl, propyl, butyl, pentyl or hexyl. More preferably, X is selected from the group consisting of fluorine and chlorine and R ^{2 is} selected from the group consisting of methyl and ethyl. An example of a preferred halogenated alcohol is 2,2,2-trifluoroethanol.

Other derivatives of alcohols that can be used include amines, such as methylethanolamine.

A preferred reducing agent containing at least one aldehyde group (-CHO) is selected from the group consisting of a compound having the general formula (V), an alkanedialdehyde compound having the general formula (VI), a halogenated aldehyde And other derivatives of aldehydes.

Therefore, in certain embodiments, the reducing agent is an aldehyde having the general formula (V): R ³ -CHO (V)

Wherein R ^{3 is} selected from the group consisting of hydrogen and straight-chain or branched C1-C20 alkyl and alkenyl, preferably methyl, ethyl, propyl, butyl, pentyl, or hexyl. More preferably, R ^{3 is} selected from the group consisting of methyl or ethyl. Examples of preferred compounds according to formula (V) are formaldehyde, acetaldehyde and butyraldehyde.

In other examples, the reducing agent is an aldehyde having the general formula (VI): OHC-R ⁴ -CHO (VI)

Wherein R ⁴ is a linear or branched C ₁ -C ₂₀ saturated or unsaturated hydrocarbon. Alternatively, the aldehyde groups may be directly bonded to each other (R ^{4 is} not present).

The reducing agent containing at least one -COOH group may be selected from the group consisting of compounds of general formula (VII), polycarboxylic acids, halogenated carboxylic acids, and other derivatives of carboxylic acids.

Therefore, in certain embodiments, the preferred reducing agent is a carboxylic acid having the general formula (VII): R ⁵ -COOH (VII)

Among them, R ⁵ is hydrogen or a linear or branched C ₁ -C ₂₀ alkyl or alkenyl group, preferably methyl, ethyl, propyl, butyl, pentyl or hexyl, more preferably methyl or ethyl base. Examples of preferred compounds according to formula (VII) are formic acid and acetic acid, most preferably formic acid (HCOOH).

In some embodiments, a third reactant is used in the atomic layer deposition cycle. In certain embodiments, a nickel thin film deposited atomic layer deposition type process include nickel reactant, an organic reducing agent or hydrogen and synthesis gas (e.g., contained in the N ₂ 5% or 10% H ₂₎ alternating And continuous pulses.

In embodiments where titanium oxide is formed, exemplary oxygen reactants that may be used include, but are not limited to, water, ozone, oxygen plasma, oxygen radicals, or oxygen atoms.

In embodiments where nickel nitride is formed, exemplary nitrogen reactants that can be used include NH ₃ , N-containing plasmas, N / H-containing plasmas.

Examples

The growth of nickel and Ni _x N _y was investigated in both the F-120 reactor and the Pulsar ^® 2000 reactor. At the same time, two test piece substrates (5 × 5 cm 2) were loaded into the F-120 reactor. The test was performed using a first substrate including a first surface of SiO ₂ and a second surface of HF-etched silicon and a second substrate including a surface of HF-etched silicon in the same deposition process. The first substrate including the SiO ₂ surface is masked and etched with HF to form a SiO ₂ first surface 710 and an H-terminated second surface 720. The reaction temperature was set to 300 ° C, and the bis (4-N-ethylamino-3-pentene-2-N-ethylimine group was used by a pulsed chemical vapor deposition process as described herein. ) Nickel (II) grows nickel as a nickel precursor. The chemical vapor deposition process includes 1500 pulse and purge steps. No second reactant is pulsed into the reaction chamber. As shown in FIG. 7, nickel is selectively deposited on the first surface 710 of SiO ₂ (as opposed to the second surface 720 etched by HF (Si-H)) of the first substrate. No nickel is deposited on the second substrate including the HF-etched silicon surface. Therefore, the deposition temperature is high enough to achieve the decomposition of the nickel precursor on the Si-OH-terminated surface (such as the first surface 710) rather than on the Si-H-terminated surface (such as the second surface 720).

It was also tested in a Pulsar ^® 2000 reactor and the deposition was performed according to a process as described herein by pulsing the nickel precursor and the NH ₃ second reactant 4000 times at a temperature of 300 ° C. No film was observed on the 200 mm silicon wafer etched by HF, while a Ni _x N _y film was deposited on the first surface of the 200 mm wafer containing SiO ₂ (relative to the second surface containing silicon).

Another test was also performed in a Pulsar ^® 2000 reactor, using bis (4-N-ethylamino-3-pentene-2-N-ethylimino) nickel (II) as the nickel precursor And perform the deposition. The chemical vapor deposition process includes 5000 pulses and a purge step at a reaction temperature of 300 ° C., each pulse has a duration of about 1 second, and each purge step has a duration of about 5 seconds. Nickel is selectively deposited on the first surface of SiO _{2 of the} first substrate (the second surface subjected to HF etching (Si-H) with respect to the second substrate). XPS analysis confirmed the deposition of nickel on the SiO ₂ surface. No nickel is deposited on the second substrate including the HF-etched silicon surface. Therefore, the deposition temperature is high enough to achieve decomposition of the nickel precursor, for example, on a Si-OH-terminated surface instead of, for example, a Si-H-terminated surface.

Relative to SiO ₂ Selectively grow SiO on Si-H ₂

The surface ₂ SiO (terminated surface with respect to H (e.g. _{-SiH. 3,} -SiH ₂ -SiH or surface)) comprises selectively deposited on nickel, titanium, iron, or cobalt material (such as nickel, a nickel nitride, (Or titanium oxide) allows selective growth of SiO ₂ on the H-terminated surface. In certain embodiments, with respect to the second H surface as described herein is end-capped, as in the first selectively surface (e.g. the surface of SiO ₂₎ is deposited on the article comprises a nickel, titanium, iron, or after the material of cobalt, relative to the first surface may then (for example, nickel, NiN _x, iron, or cobalt, or titanium oxide surface), a second H surface selectively (e.g. -SiH _3, -SiH ₂ capped, depositing surface or -SiH) SiO _2. SiO ₂ can be deposited by any method known in the art (e.g., by enhanced atomic layer deposition using oxygen radicals, plasmas, or plasmas of atomic oxygen, or by thermal atomic layer deposition using, for example, ozone ). In some embodiments, both a thermal atomic layer deposition process and a plasma atomic layer deposition process are utilized. Silicon precursors known in the art can be used. In some embodiments, the silicon precursor may include (R ^I R ^II N) ₂ SiH ₂ , X _y SiH _4-y , (R ^I R ^II N) _y SiH _4-y , or (R ^I R ^II N ) SiH ₃ , wherein R ^I and R ^{II are} preferably independently selected from C ₁ -C ₅ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and X may Is, for example, a halide. In some embodiments, SiO ₂ is formed by exposing the substrate to an oxygen plasma.

After selectively growing a desired thickness of SiO ₂ on the second surface (as opposed to the first surface), the nickel, titanium, iron, or cobalt containing nickel, titanium, iron, or cobalt previously deposited on the first surface can be removed, for example, by etching. material. The etching process preferably completes the newly formed SiO ₂ layer on the second surface. ₂ having a first surface by the barrier material comprises a nickel, titanium, iron, or cobalt SiO, with respect to the surface of the SiO ₂ is blocked selectively in the surface of H-terminated (e.g. -SiH, -SiH _2, or - SiH ₃ surface) forms SiO ₂ .

In some embodiments, the etching step includes exposing the substrate to a selective metal etch (eg, HCl or piranha (H ₂ SO ₄ : H ₂ O ₂ ) immersion solution). For example, the substrate can be immersed in a dilute HCl and / or HNO ₃ aqueous solution or piranha etch, which can etch most metals, including nickel, without silicon, silicon oxide, or other Non-metallic materials cause significant corrosion.

Claims (25)

A deposition method includes providing a substrate including a first surface and a chemically different second surface, wherein the first surface includes at least one AHx end cap, wherein A is one or more of nitrogen, oxygen, or sulfur And x is 1 to 2, and the second surface is a SiH _x hydrogen-terminated surface, where x is 1 to 3; and contacting the first surface and the second surface of the substrate with nickel, A first gas phase precursor of titanium, iron, or cobalt; thereby selectively depositing nickel, titanium, iron, or nickel on the first surface of the substrate with respect to the second surface of the same substrate Cobalt material. The deposition method according to item 1 of the patent application range, wherein the material selectively deposited includes nickel or cobalt. The deposition method according to item 1 of the patent application scope, wherein the selective deposition further comprises: contacting the substrate with a second gas-phase reactant. The deposition method according to item 1 of the scope of patent application, wherein the second surface of SiH _x hydrogen termination is formed by processing at least a portion of the surface of the substrate before depositing the material. The deposition method according to item 1 of the scope of patent application, wherein the second surface of SiH _x hydrogen termination is formed by processing at least a portion of the surface of the substrate with hydrofluoric acid etching. The deposition method according to item 1 of the patent application scope, wherein the second surface of SiH _x hydrogen termination is formed by processing at least a portion of the surface of the substrate with a silicon compound including ClSiH ₃ Or (R ^I R ^II N) SiH ₃ , wherein R ^I and R ^{II are} independently C ₁ -C ₄ alkyl. The deposition method according to item 1 of the patent application scope, wherein the first surface includes at least one OH end cap. The deposition method as described in claim 1, wherein the first surface includes SiO ₂ . The deposition method according to item 1 of the patent application scope, wherein the first surface is a low-K insulator. The deposition method according to item 1 of the patent application scope, wherein the first surface comprises silicon oxide, silicon nitride, silicon oxynitride, fluorosilicate glass, carbon-doped silicon oxide, or another material containing at least 50% silicon oxide. One material. The deposition method according to item 1 of the patent application scope, wherein the second surface comprises -SiH ₃ , -SiH ₂ or -SiH surface capping. The deposition method according to item 1 of the patent application scope, wherein the first surface containing nickel, titanium, iron is selectively deposited on the first surface with a selectivity of at least 90% relative to the second surface of the SiH _x hydrogen end cap. Or cobalt of the material. The deposition method according to item 1 of the scope of patent application, wherein the method for depositing the material is an atomic layer deposition or chemical vapor deposition process. A method for selectively depositing a material including nickel, titanium, iron, or cobalt on a substrate, the method comprising: providing a substrate including a first surface, the first surface including silicon oxide; and etching the first surface At least a portion to thereby provide a second hydrogen-terminated silicon surface; and selectively depositing nickel, titanium, iron, or cobalt on the first surface of silicon oxide relative to the second hydrogen-terminated silicon surface material. The method for selectively depositing a material including nickel, titanium, iron, or cobalt on a substrate as described in item 14 of the scope of patent application, wherein the selectively depositing the material including nickel, titanium, iron, or cobalt includes: selecting It is deposited until the desired material comprising nickel, titanium, iron or cobalt is formed. The method for selectively depositing a material containing nickel, titanium, iron, or cobalt on a substrate as described in item 14 of the patent application scope, wherein the selectively depositing a material containing nickel, titanium, iron, or cobalt on a substrate The method is an atomic layer deposition or chemical vapor deposition process. The method for selectively depositing a material including nickel, titanium, iron, or cobalt on a substrate as described in item 14 of the scope of patent application, wherein etching at least a portion of the first surface includes: The part was exposed to hydrofluoric acid. The method for selectively depositing a material containing nickel, titanium, iron, or cobalt on a substrate as described in item 14 of the scope of patent application, wherein the second hydrogen-terminated silicon surface, The material comprising nickel, titanium, iron or cobalt is selectively deposited on the first surface. A method for selectively forming SiO ₂ on a substrate, including: selectively depositing nickel, titanium, iron, or nickel on the first surface of the substrate with respect to a second hydrogen-terminated silicon surface of the same substrate. A material of cobalt, wherein the first surface includes at least one AH _x end cap, wherein A is one or more of oxygen, nitrogen, and sulfur, and x is 1 to 2; A first surface selectively deposits SiO ₂ on the second hydrogen-terminated silicon surface of the substrate. The method for selectively forming SiO ₂ on a substrate according to item 19 of the scope of patent application, wherein the method further comprises: etching the substrate to remove nickel, titanium, iron, or cobalt containing the substrate from the substrate.所述 材料。 The material. The method for selectively forming SiO ₂ on a substrate according to item 20 of the patent application scope, wherein etching the substrate comprises: exposing the substrate to HCl, HNO ₃ or H ₂ SO ₄ : H ₂ O ₂ At least one of them. The method for selectively forming SiO ₂ on a substrate as described in item 19 of the scope of patent application, wherein the first surface includes an OH-terminated surface. The method for selectively forming SiO ₂ on a substrate as described in item 19 of the scope of patent application, wherein the first surface includes silicon oxide. The method for selectively forming SiO ₂ on a substrate as described in item 19 of the scope of the patent application, wherein the second hydrogen-terminated silicon surface includes -SiH, -SiH ₂ or -SiH ₃ surface termination. The method for selectively forming SiO ₂ on a substrate as described in item 19 of the scope of patent application, wherein a plasma-enhanced atomic layer deposition or thermal atomic layer deposition process is selectively performed on the first surface with respect to the first surface. SiO ₂ is deposited on the second hydrogen-terminated silicon surface of the substrate.